Manufacture of modified basic polyaminoamide with ammonium compound

ABSTRACT

A process for the production of water-soluble auxiliary agents based on polyaminoamides by reacting a polyfunctional compound with a tertiary, monofunctional amine to form an ammonium compound and reacting that ammonium compound with a basic polyaminoamide, the basic polyaminoamide being the polycondensation product of a dicarboxylic acid, a polyalkylenepolyamine and an aminocarboxylic acid or lactam thereof, the basic polyaminoamide being reacted with 0.15 to 0.19 mol of a polyfunctional compound per mol equivalent of secondary amino group in the polyamide, incorporating that modified basic polyaminoamide in the paper pulp so as to increase the retention of fibres, fillers or pigments, or to accelerate the drawings.

PRIOR ART

This invention relates to a process for the production of basic,storage-stable polyaminoamides which can be reacted with thepolyfunctional compounds and which are suitable as retention agents forfillers and pigments, as drainage accelerators and as agents fortreating effluents in the manufacture of paper.

Suitable processes of this kind are already known for the preparation ofsuch products which can be used as auxiliaries in the manufacture ofpaper.

Thus U.S. Pat. No. 3,320,215 discloses that aminocarboxylic acids orlactams thereof can be polycondensed with dicarboxylic acids andpolyalkylenepolyamines and can be crosslinked with epichlorohydrin.

A condensate composed of polyalkylenepolyaminodicarboxylic acids, whichhas been reacted with epichlorohydrin, is also disclosed in BritishPatent Specification No. 865,727.

British Patent Specification No. 1,035,296 also discloses reactionsbetween epichlorohydrin and polyaminoamides which have been preparedfrom dicarboxylic acids and polyalkylenepolyamines. These products areat least relatively stable on storage.

Finally, German Auslegeschrift No. 1,771,814 has disclosed the use ofbasic polyamides for increasing the retention of fillers and pigments inthe manufacture of paper, for accelerating the drainage of suspensionsof raw materials for paper and for working up effluents from papermachines by filtration, sedimentation and flotation, by the addition ofbasic polyamides to the suspensions of raw materials for paper and/oreffluents from paper machines, the basic polyamides used being highmolecular, water-soluble reaction products, which have been obtained bythe action of compounds which are polyfunctional towards amino groups,on basic polyamides composed of polyfunctional amines, dicarboxylicacids and aminocarboxylic acids containing at least three carbon atoms,or their lactams, dissolved or dispersed in water, and for thepreparation of which less than one equivalent of reactive groups in thepolyfunctional compounds has been used for one equivalent of the basicamino groups contained in the basic polyamides.

All the products disclosed by the abovementioned state of the art are,however, insufficiently stable on storage in a basic medium, and theirfunction as a retention agent in the sense mentioned above is notsatisfactory.

In using these crosslinked polyaminoamides in the paper industry forraising the retention of fillers, pigments and fibres and foraccelerating the drainage of suspensions of raw materials for paper, itis necessary for these polyaminoamides to be compatible with the basicproducts based on polyethyleneimine, which possess a similar functionand are often admixed, that is to say these polyaminoamides must possessan adequate stability on storage in this basic medium. If, as with theproducts disclosed by the abovementioned state of the art, this is notthe case, these products are completely gelled in the presence ofalkaline solutions of polyethyleneamine, as a result of which problemsarise in the manufacture of paper, because the paper web is notsufficiently drained.

OBJECT OF THE INVENTION

It is therefore an object of the invention to provide a suitable processfor the production of a retention agent which, in respect of processconditions, exhibits an improved retention and performance inaccelerating drainage in the manufacture of paper and, furthermore, isstable in an alkaline medium.

THE INVENTION

Accordingly this invention relates to a process for the production of amodified basic polyaminoamide which comprises the steps of (a) reactinga polyfunctional compound with a tertiary, monofunctional amine to forman ammonium compound and (b) reacting 0.2-1.8 mols of the ammoniumcompound with each mol of secondary amino group in a water-soluble,basic polyaminoamide, the basic polyaminoamide being a condensationproduct of a member selected from the class consisting of dicarboxylicacids, a member selected from the class consistiong ofpolyalkylenepolyamines and a member selected from the class consistingof amino carboxylic acids and lactams, the basic polyaminoamide beingreacted with 0.15-0.19 mol of a polyfunctional compound per molequivalent of secondary amino groups in the polyaminoamide. In the saidprocess a tertiary, monofunctional amine is a member, selected from agroup which comprises trimethylamine, triethylamine, tripropylamine,tributylamine, dimethylaniline or dimethylcyclohexylamine or a mixtureof any thereof. Moreover, in said process 1 mol of the polyfunctionalcompound and 1 mol of the tertiary, monofunctional amine are reacted.

The effect of a reaction product made from the polyfunctional compound,such as, for example, epichlorhydrin or dichlorhydrin, and from atertiary, monofunctional amine, such as, for example, tirmethylamine,triethylamine, tripropylamine, tributylamine, triethanolamine,dimethylaniline and dimethylcyclohexylamine, is to obtain and maintainthe positively charged character of the basic polyaminoamide, whichproducts an improvement of the retention, acceleration of drainage,sedimentation and flotation of suspensions of raw materials for paperand/or of effluents from paper machines. The product, obtained by theprocess according to the invention comprises modified basicpolyaminoamides, which are a reaction product of a (a) polyfunctionalcompound, selected from the class consisting of epichlorhydrin anddichlorhydrin or a mixture thereof, (b) a tertiary, monofunctionalamine, selected from a group which comprises trimethylamine,triethylamine, tripropylamine, tributylamine, dimethylaniline ordimethylcyclohexylamine or a mixture of thereof, (c) a basicpolyaminoamide as a condensation product of (I) a member selected from agroup, which comprises dicarboxylic acids, (II) a member selected from agroup comprises polyalkylenepolyamines and (III) a member selected froma group, which comprises aminocarboxylic acids and lactams; and whereinsaid reaction product (a, b, c) has been reacted with 0.15-0.19 mol of apolyfunctional compound per mol equivalent of secondary amino group inthe polyaminoamide.

The effect of a reaction product of this compound is to obtain andmaintain the positively charged character of the basic polyaminoamide,which products an improvement of the retention, acceleration ofdrainage, sedimentation and flotation of suspensions of raw materialsfor paper and/or effluents from paper machines. In addition, as afurther advantage, it should be noticed that the product obtained by theprocess according to the invention has a surprisingly good stability onstorage, especially in a basic medium. At the close of the manufacturingprocess, therefore, it is no longer necessary, as it has been hitherto,to acidify the product obtained so that it does not gel prematurely orotherwise becomes unusable as a retention agent in the sense previouslymentioned. The same advantages result, if, instead of one tertiaryamine, several of the abovementioned amines are mixed and this mixtureis reacted with polyfunctional compounds such as epichlorohydrin ordichlorohydrin, or these products are allowed to act upon one another. Aparticularly preferred manufacturing process is one in which atrialkylamine is used as the tertiary, monofunctional amine which istreated with one mol equivalent of the polyfunctional compound and thenreacts with a basic polyaminoamide which reacts with 0.16-0.18 mol ofepichlorohydrin per mol of secondary amino groups in the polyaminoamide.

Products of this kind can be stored particularly well even in analkaline medium or can be mixed with polyethyleneimines or with otherbasic materials used in the manufacture of paper, without the occurrenceof gelling or other disadvantageous changes. In addition, they exhibit aparticularly high retention effect. Therefore a method lies within thescope of the invention, in which the retention of fibres, fillers orpigments or accelerating drainage or working up effluent in papermanufacture is increased, that method comprises incorporating a modifiedbasic polyaminoamide into the paper pulp or into the paper manufactureeffluent.

The invention is now illustrated in relation to the following examples,but is not limited to these.

EXAMPLE 1 ACCORDING TO THE INVENTION

In order to prepare the reaction product of epichlorohydrin andtrimethylamine, 187.7 kg of 33% strength by weight trimethylamine wererun into a steel vessel of 300 l capacity, fitted with a stirrer andtemperature point. 97.0 kg of epichlorohydrin were then added slowlywith stirring and cooling, from a supply vessel. The temperature rose to65° C. The reaction product was kept at this temperature for a further 2hours, while stirring, and the reaction was then completed by cooling.

284.7 kg of end product ≃ 1,048.5 mols were obtained. The chlorine splitoff, which is present in the solution as chloride, was 99.5% of theory,relative to epichlorohydrin. The pH was about 11.20.

Separately from this, 79.4 kg. corresponding to 770 mols, ofdiethylenetriamine, 103.1 kg ≃ 706 mols of adipic acid and 15.98 kg =140 mols of caprolactam were run, with stirring, into a steel autoclaveof 300 l capacity, fitted with a stirrer, a temperature point and a sidecondenser. The mixture of monomers was then heated to 165° C. as aresult of which there was a slight excess pressure. 120 kg of water ofcondensation were distilled off from the mixture over the course of 2hours. The reaction temperature was then raised to 185° C. and thesecondary condensation was continued for a further 2 hours while passingnitrogen through at a rate of 80 l/hour. Altogether, 24.5 kg of waterwere distilled off. After the polycondensate had been cooled, 123 l ofwater were added as diluent.

An intermediate analysis gave the following results.

Concentration: 50.05% by weight

pH value: 11

Amine number: 278 mg of KOH/g of polyconsate (PC)

Viscosity at 20° C.: 200 cP

The whole polycondensate solution was then transferred into a 1,200 lsteel vessel fitted with a stirrer and temperature point. The solutionof the polyamide was diluted with water to 25% strength by weight andwas then heated to 60° C. and 41.82 kg = 0.200 mol per 1 mol equivalentof secondary amino groups of the abovementioned reaction product oftrimethylamine and epichlorohydrin were then added to the solution ofpolycondensate. After 1 hour of addition reaction, the increased solidscontent was once more adjusted with water to 25% strength by weight.

Finally, the reaction product was crosslinked with 11.967 kg≃ 0.168 molper 1 mol equivalent of secondary amine groups, of epichlorohydrin, theepichlorohydrin being added slowly to the solution and the reactionmixture being kept continuously stirred at a speed of 100 revolutionsper minute.

After a reaction time of altogether 7.5 hours at a reaction temperatureof 60° C., the flow time of the product was measured in accordance withDIN A 53,211, with the aid of a Frikmer cup. Under these conditions theflow time was 34 seconds.

The finished product, thus measured and fixed, was then again dilutedwith water to 20% strength by weight and was cooled.

The final analysis of the product thus obtained gave the followingresults:

Concentration in the aqueous solution: 20.25% by weight

pH value: 9.0

Amine number: 153 mg of KOH/g of PC

Viscosity: 178 cP

Appearance: faintly yellow solution.

EXAMPLE 2 ACCORDING TO THE INVENTION

The polycondensate was prepared as described in Example 1 and usingexactly the same quantities. The solution was also diluted with water to25% strength by weight and heated to 60° C. 11.967 kg (≃ 0.168 mol/1 molequivalent of secondary amine group) of epichlorohydrin were thenintroduced slowly under the stirring conditions described. After areaction time of 73/4 hours at 60° C., it was possible to measure a flowtime of 34.5 seconds, which did not change even after a furtheradditional reaction phase.

41.82 kg (≃ 0.200 mol/1 mol equivalent of secondary amine group) of thereaction product according to Example 1 were now introduced into theviscous solution. After an addition reaction time of 1 hour, the Frikmercup gave a flow time of 32 seconds, which did not alter even during anadditional reaction time of 1 hour. The end product was adjusted to 20%strength by weight.

The analysis gave the following results:

Concentration: 20.15% by weight

pH value: 9.10

Amine number: 149 (mg of KOH/g of PC)

Viscosity (20° C.): 172 cP

Appearance: clear, slightly yellow solution.

Table 1 which follows lists further examples according to the inventionin order to represent the different quantities used of the reactionproduct of trimethylamine and epichlorohydrin according to Example 1.

The quantities of the polycondensate used corresponded to thoseaccording to Example 1.

The modification and crosslinking were carried out as can be seen inExample 1.

                                      Table 1                                     __________________________________________________________________________    Quantity used of                                                                          Molar ratio of                                                                           1 mol equi- Final analysis                                reaction product                                                                       reaction product                                                                         valent of sec-  concentration                                                                         Viscosity                      Ex.                                                                              according to Ex.                                                                       according to                                                                             ondary amine                                                                          pH  amine                                                                             (% by   (cP) (20° C)            No 4a (kg)  Ex. 4a   / group   value                                                                             number                                                                            weight) by Hoppler                     __________________________________________________________________________    3  125.46   0.600    / 1       8.9 140 20.1    168                            4  250.9    1.200    / 1       9.1 129 20.2    181                            5  376.4    1.800    / 1       9.2 119 20.05   175                            __________________________________________________________________________

COMPARISON EXAMPLE 1 (DAS No. 1,771,814) ≃ REACTION PRODUCT 1

a. 108 g (1.05 mols) of diethylenetriamine, 146 g (1 mol) of adipic acidand 57 g (0.5 mol) of caprolactam, mixed with 7 g (0.04 mol) of adipicacid hydrazide, are introduced into a reaction flask fitted with astirrer, a thermometer and a side condenser. The mixture of monomers isheated to 150° C. over the course of 3 hours while passing N₂ throughand stirring, approx. 35 g of water being distilled off. After applyinga vacuum of approx. 20 mm Hg, the reaction is continued until approx. 50ml of distillate have been collected. The product is cooled to approx.120° C. and diluted with 270 g of water to 50% strength by weight.

b. 420 g of this 50% strength solution of polycondensate are heated to85° C. with 428 g of water and 16.8 g (≃ 0.21 mol/1 mol equivalent ofsecondary amine group) of 1,2-dichloroethane in another reaction flaskhaving a reflux condenser, and the mixture is stirred at thistemperature until the viscosity of the solution has reached approx. 250cP at 80° C. (measured in a Hoppler viscometer), which, in the case ofour repetition, was the case only after more than 12 hours. The productwas treated as described with 150 g of water and approx. 60 g ofconcentrated hydrochloric acid and was cooled. The pH value was 3.9 andthe concentration was 20.1% by weight. The Hoppler viscosity was 240 cPat 25° C. A sample taken before the addition of the hydrochloric acidwas completely gelled after 2 hours.

COMPARISON EXAMPLE 2 (U.S. Pat. No. 3,320,215) ≃ EXAMPLE 1

93 g (0.9 mol) of diethylenetriamine, 20 g (0.136 mol) oftriethylenetetramine and 50 g of water are run into a round flask havinga stirrer, thermometer and condenser. 20 g (0.177 mol) of caprolactamand 145 g (1 mol) of adipic acid are added to this solution. The mixtureof monomers is then heated with stirring and the quantity of water whichis theoretically liberated is distilled off at 195° C. over 3.5 hours. Avacuum is then additionally applied for 1/2 hour at 180°-190° C., inorder to complete the reaction. The product is cooled to approx. 140° C.and 385 g of water are added in portions. The diluted solution has aconcentration of 36.85% by weight.

91 g of this solution are withdrawn and mixed with 263 g of water andheated to 50° C. in a round flask, while stirring. 16.0 g ofepichlorohydrin are now added dropwise, the solution of condensate beingheated to 65° C.

After a period of approx. 2.5 hours, the Gardner viscosity as given inUS-PS Example 1 (≃ approx. 250 cP) had been reached, a sample waswithdrawn and the product was diluted with 150 g of water, cooled andadjusted to pH 4 with concentrated hydrochloric acid. The concentrationwas 10.5% by weight. The sample taken had a pH value of 6.8 and hadbecome gel-like after 8 days.

COMPARISON EXAMPLE 3 (≃ EXAMPLE 1 of U.S. Pat. No. 3,086,961)

146 g (1 mol) of adipic acid and 103.2 g (1 mol) of diethylenetriaminewere mixed in a round flask having a condenser, thermometer and stirrerand were heated to 165° C. while passing N₂ through and stirring wascontinued until 35 ml of water had been distilled off, which was thecase after 2.5 hours. The solution was then cooled. The polycondensatewas diluted with water to 30% strength by weight and was heated to 60°C. 10 mol% of epichlorohydrin (≃ 0.100 mol/l secondary amine group ≃9.25 g of epichlorohydrin) were then added to the polycondensatesolution. The viscosity was measured after 2, 4, 6, 8 and 10 hours; as,however, no alteration of the initial viscosity could be obtained in anycase, the reaction was discontinued after 10 hours and the product wascooled. The viscosity, measured by Hoppler's method, was only 45 cP at20° C. and the concentration was 30.4% by weight.

As can be seen in the preceding comparison example, the similarlyprepared polycondensate solution was also diluted to 30% strength byweight with water and heated to 60° C. in accordance with Example 3 ofthe abovementioned US-PS. 20 mol% of epichlorohydrin (≃ 0.200 mol/lsecondary amine group ≃ 18.50 g of epichlorohydrin) were now added tothe polyamide solution. After stirring for 2.5 hours, a viscosity of 160cP (Hoppler, 20° C.) was measured, ≃ approx. Gardner-Holdt G. The pHvalue of the product was immediately adjusted to 4 with concentratedhydrochloric acid and it was cooled. A sample withdrawn before theaddition of the hydrochloric acid gelled completely after 1 hour.

The end product which had been treated with hydrochloric acid had aconcentration of 30.8% by weight and a Gardner-Holdt viscosity between Fand G, ≃ 150 cp (20° C.) measured in the Hoppler viscometer.

COMPARISON EXAMPLE 4 (≃ EXAMPLE 6 of GB-PS No. 1,035,296)

183 g (1.25 mols) of triethylenetetramine and 183 g (1.35 mols) ofadipic acid were mixed in a round flask (in accordance with the otherexamples), were heated to 150° C. while stirring and passing N₂ throughand were allowed to condense for 2 hours.

After cooling, the solution was diluted with water to 35% strength byweight and was once more heated to 80° C. 14 g of epichlorohydrin werethen added and the mixture was kept at 80° C. for approx. 90 minutes,while stirring. A further, calculated 3.20 g of epichlorohydrin,corresponding to the described ratio of 0.09 mol ofepichlorhydrin/secondary amine group, was additionally run into thesolution (in accordance with Example 6 of GB-PS No. 1,035,296 andExample 1 of U.S. Pat. No. 3,086,961).

The reaction was continued for a further 2 hours; as, however, noincrease in the viscosity could be detected and measured, the productwas cooled and adjusted to pH 4 with hydrochloric acid as described.

It therefore appeared, that the viscosity before the addition of thequantity of epichlorohydrin and after the phase of the reactiondescribed, had not altered (as indeed would be expected).

Use Example 1

The products mentioned from the examples prepared in accordance with theinvention and from the comparison examples were tested as follows toassess their drainage capacity. The time of drainage was determined bymeans of the Schopper-Reigler apparatus in accordance with the pamphletV/7/61 (Verein der Zellstoff- und Papier-Chemiker und -Ingenieure("Association of Pulp and Paper Chemists and Engineers")).

Working principle

The bottom outlet socket of the Schopper-Riegler apparatus is closedwith a stopper. 3.0 g of dry fibre pulp, uniformly dispersed in apulp-water volume of 1,000 ml (at 20°), are discharged from thecontainer of the apparatus onto the wire by opening the bottom valve,whereupon the pulp-water mixture drains more or less rapidly.

The water which flows away emerges through the side outlet. The time inseconds, during which the 700 ml of water emerge from the side outlet,is determined, measured from the instant of lifting the bottom valve.The fibre pulp used was newsprint of uniform consistency, comminutedmechanically. Since 0.1 - 0.3% by weight of additives (relative to dryfibres) consisting of retention and drainage auxiliaries is customarilyused in the production of paper, these quantities of additives were alsoused as a basis in this series of tests.

Table II which follows summarises the results of all the productstested.

0.2% strength by weight solutions were made up of the products preparedin accordance with the examples according to the invention and thecomparison examples. Before the fibre pulp-water volume was poured intothe flow cup, 1 ml ≃ 0.1% strength by weight, 2 ml ≃ 0.2% strength byweight and 3 ml ≃ 0.3% strength by weight of the solutions prepared wereappropriately added as drainage auxiliaries.

Table II clearly shows the superiority of the products according to theinvention in respect of drainage capacity, compared with the products ofwhich the preparation was repeated in the comparison examples.

                                      Table II                                    __________________________________________________________________________    Increase in drainage capacity in %, relative to the initial drainage          capacity                                                                      (standard) when adding the products of the invention and the comparison       products (solutions) in:                                                      __________________________________________________________________________    Example No. 0.10% strength by weight                                                                    0.20% strength by weight                                                                    0.30% strength by                     __________________________________________________________________________                                            weight                                1 (according to                                                                           76            80            85                                      the invention)                                                              2 (according to                                                                           71            76            79                                      the invention)                                                              3 (according to                                                                           70            75            79                                      the invention)                                                              4 (according to                                                                           74            73            83                                      the invention)                                                              5 (according to                                                                           73            76            82                                      the invention)                                                              1 (comparison                                                                             67            70            73                                      example)                                                                    2 (comparison                                                                             64            68            71                                      example)                                                                    3 (Example 1 of                                                                           20            22            25                                      US-PS 3,086,961)                                                            3 (Example 3 of                                                                           60            64            67                                      US-PS 3,086,961)                                                            4           18            21            22                                    __________________________________________________________________________

Use Example 2

So-called "corrugated material" was prepared on a production papermachine from ground waste paper without additives which influence thepH-value. Operations were carried out in the neutral range with a closedcirculation of water. The drainage and retention auxiliary agent usedwas a known commercial product of the "polyethyleneimine" class, addedbefore the headbox in an amount of 0.3% by weight, relative to drymaterial, by means of a metering pump installation having a capacity of100 strokes/minute. The speed of the paper machine was 227 m/minute; thebackwater had a temperature of 40° C. and a pH value of 6.

With these machine conditions, a change was now made, at the samedosage, from the commercial product to the drainage and retentionauxiliary agent prepared, in Example 1 according to the invention. Aftera production running time of 3 hours, no adverse changes of any kindcould be observed in the machine. A sample of the dry corrugatedmaterial was taken for ash determination and a sample of the effluentwas taken to determine the retention effect.

The remaining products according to the invention from Example 1 - 5 andthe products from the Comparison Examples 1 -4 were also tested on thispaper machine analogously to this procedure and corresponding sampleswere taken.

With the products from the Comparison Examples 3 (Example 1) and 4, itwas necessary to discontinue their use on the paper machine after quitea short time, because the drainage of the products and the retentionbecame so poor that an interruption of production would have beeninevitable.

It was therefore not possible to employ these 2 comparison products fordetermining the retention effect on the paper machine. As ashdetermination was carried out on the samples of paper obtained from theproducts mentioned, which were used in accordance with the invention,and from the remaining comparison products.

At the same time, the samples of effluent (backwater) which were takenin parallel, were examined for solids content (dry residue). Bothdeterminations are a measure of the retention effect. The results aresummarised in Table III which follows.

For comparison, the retention and drainage auxiliary agent customarilyused in production -- Tydex 16 -- of Messrs. Dow Chemical(polyethyleneimine) was also examined and is included in Table III.

                                      Table III                                   __________________________________________________________________________                  Ash content of the paper,                                                                   Dry residue in effluent,                          Example No.   in % by weight                                                                              in g/l                                            __________________________________________________________________________    Invention example                                                                         1 6.22          1.500                                                         2 6.20          1.520                                                         3 6.19          1.480                                                         4 6.17          1.460                                                         5 6.18          1.500                                             Comparison example 1                                                          DAS 1,771,814                                                                             5.88                                                                            1.740                                                           Comparison example                                                                        2                                                                 US-PS 3,320,215                                                                             5.80          1.810                                             Comparison example                                                                        3                                                                 (US-PS 3,086,961 (see                                                                       5.83          1.840                                             Example 3 therein)                                                            Commercial product                                                                          5.92          1.650                                             "Tydex 16"                                                                    __________________________________________________________________________

Use Example 3

It is intended to show in this example that the basic products preparedin accordance with the invention are also stable on storage for a longerperiod and that their viscosity state does not alter. The flow time wastested in the Frikmer cup already mentioned, at 20° C. over the courseof 12 weeks, at intervals of 2 weeks. The results are summarised inTable IV.

                  Table IV                                                        ______________________________________                                        Product                                                                       from Example                    measured                                      according to the                                                                         Flow time in seconds (20°  C.)                                                              after:                                        invention No.                                                                            2      4      6    8    10     12 weeks                            ______________________________________                                        1          38     38     38.4 38.4 38.4   38.4                                2          37.5   37.8   37.9 37.9 37.9   37.9                                3          34     34.2   34.2 34.2 34.2   34.2                                4          39.2   39.5   39.5 39.5 39.5   39.5                                5          38.2   38.2   38.4 38.4 38.4   38.4                                ______________________________________                                    

USE EXAMPLE 4

In this example it is intended to demonstrate the perfect compatibilityand stability on storage of the products prepared in accordance with theinvention, with the known basic polyethyleneimine products which areavailable commercially.

The acid comparison products the preparation of which was repeatedaccording to the state of the art, were also included in the test.

The following polyethyleneimines (commercial products) were employed forthe mixture:

Tydex 16: of DOW Chemical

Polymin SN: of BASF.

The polyethyleneimines were mixed with the products listed in Table V inproportions of 75% by weight and 25% by weight. The flow time in aFrikmer cup was then measured again over a period of 12 weeks atintervals of 2 weeks.

As no increase in viscosity was obtained with the products prepared inthe Comparison Examples 3 (Example 1) and 4, the latter are not takeninto accout in Table V.

                                      Table V                                     __________________________________________________________________________    Test of compatibility and stability on storage using commercial products      of a basic nature                                                             __________________________________________________________________________    Products                                                                      from in-                                                                      vention                                                                              Flow time in the Frikmer cup in seconds at 20° C., measured            after:                                                                 Example  2        4         6        8        10       12 weeks               No.    A   B    A   B     A   B    A   B    A   B    A    B                   __________________________________________________________________________    1      74.8                                                                              144.2                                                                              74.4                                                                              143.6 74.2                                                                              143.5                                                                              74.2                                                                              143.5                                                                              74.2                                                                              143.5                                                                              74.2 143.5               2      70.6                                                                              143.5                                                                              70.2                                                                              143.0 70.0                                                                              142.8                                                                              70.0                                                                              142.8                                                                              70.0                                                                              142.8                                                                              70.0 142.8               3      70.2                                                                              143.1                                                                              69.7                                                                              142.9 69.6                                                                              142.6                                                                              69.5                                                                              142.5                                                                              69.5                                                                              142.5                                                                              69.5 142.5               4      75.0                                                                              146.8                                                                              74.6                                                                              146.0 74.4                                                                              145.8                                                                              74.4                                                                              145.8                                                                              74.4                                                                              145.8                                                                              74.4 145.8               5      75.8                                                                              144.0                                                                              73.2                                                                              143.5 70.0                                                                              143.4                                                                              73.0                                                                              143.4                                                                              73.0                                                                              143.4                                                                              73.0 143.4               Compari-                                                                      son                                                                           Examples                                                                      1      G   G                                                                  2      G   G                                                                  (Example 3                                                                           G   G                                                                  of US-PS                                                                      3,086,961)                                                                    __________________________________________________________________________     Explanation: A ≈ 25% proportion of polyethyleneimine "Tydex 16" i     the corresponding product                                                     B ≈ 75% proportion of polyethyleneimine "Tydex 16" in the             corresponding product                                                         G ≈ The product mixture gelled.                                       Analogous results were obtained with the product "Polymin SN".           

If, within the scope of the abovementioned process according to theinvention, a trialkyleneamine is reacted with one mol equivalent of apolyfunctional compound or one mol equivalent of a polyfunctionalcompound is reacted and this reaction product is allowed to react with abasic polyaminoamide which, before or after this reaction, has beencrosslinked with 0.16 - 0.18 mol of epichlorohydrin per mol of secondaryamino group in the polyalkylenepolyamide, a particularly valuableproduct is obtained, because the abovementioned quantity of crosslinkingagent gives products with a particularly good retention effect andparticularly good storage stability in a basic medium. This is because,if substantially more than the abovementioned optimum quantity ofcrosslinking agent is used, the solution viscosity of the productincreases spontaneously in its solution after a certain inductionperiod. Even if only a little more than the abovementioned quantity ofcrosslinking agent is used, the solution viscosity of the product in abasic medium increases further continuously. In both cases, thiscontinuation of reactions which is indicated by a rise in the solutionviscosity can only be stopped by the addition of acids, such as, forexample, hydrochloric acid, sulphuric acid, acetic acid, formic acid andthe like.

If, on the other hand, less than the optimum quantity of crosslinkingagent is added, a noticeable increase of the viscosity does not occurnor does the product possess optimum functions for the retention effect.Only when the abovementioned optimum quantity of crosslinking agent isadded, is a solution viscosity achieved, after 2 to 10 hours, which nolonger alters, so that the aqueous solution of the product remainsstable on storage in an alkaline medium.

It has subsequently been established that the substantially optimumretention effect of the product can probably be traced back to theprocess step, according to the invention, of reacting epichlorohydrinwith trimethylamine or with another trialkylamine, with a subsequentaddition reaction with the crosslinked or uncrosslinked, basicpolyaminoamide, because the product obtained in this way has a positivecharge, which can, accordingly, be used advantageously, probably owingto the negative Zeta potential of the fibres and pigments which aresupposed to be retained in the pulp of fibre material for paper.

The synthesis of the water-soluble, basic polyaminoamides which arepolycondensed from polyalkylenepolyamines, dicarboxylic acids anddiamines, is not a subject of this invention; it is described in detailin German Offenlegungsschrift No. 2,209,242 equivalent to U.S. Pat. No.3,945,983.

I claim:
 1. A process for the production of a modified basic polyaminoamide resin which comprises the sequential steps of:a. reacting substantially equimolar portions of a polyfunctional compound selected from the group consisting of epichlorhydrin, dichlorhydrin, or mixtures thereof, with a tertiary amine selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylaniline, dimethylcyclohexylamine, or mixtures of any of said amines, to form an ammonium compound; b. reacting 0.2 - 1.8 mols of said ammonium compound with each mol of secondary amine group in a water-soluble, basic polyaminoamide which is a condensation product of1. a dicarboxylic acid,
 2. a polyalkylenepolyamine, and
 3. an aminocarboxylic acid or a lactam; and c. reacting the product of step (b) with 0.15 - 0.19 mol of said polyfunctional compound per mol equivalent of secondary amino group in said polyaminoamide.
 2. A process according to claim 1, wherein 0.16 to 0.18 mol of said polyfunctional compound per mol equivalent of secondary amino group of said polyaminoamide is reacted.
 3. A process for the production of a modified basic polyaminoamide resin which comprises the sequential steps of:a. reacting substantially equimolar portions of a polyfunctional compound selected from the group consisting of epichlorhydrin, dichlorhydrin, or mixtures thereof, with a tertiary amine selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylaniline, dimethylcyclohexylamine, or mixtures of any of said amines, to form an ammonium compound; b. reacting a water-soluble, basic polyaminoamide which is a condensation product of1. a dicarboxylic acid,
 2. a polyalkylenepolyamine, and
 3. an aminocarboxylic acid or a lactam with 0.15 - 0.19 mol of said polyfunctional compound per mol equivalent of secondary amino group in said polyaminoamide; and c. reacting the product of step (a) with the product of step (b) in the proportion of 0.2 - 1.8 mols of said ammonium compound per mol of secondary amino group in said basic polyaminoamide.
 4. The process of claim 3 wherein 0.16 to 0.18 mol of said polyfunctional compound per mol equivalent of secondary amino group of said polyaminoamide is reacted. 